CN104229789B - A kind of preparation method of nitrogen-doped graphene - Google Patents
A kind of preparation method of nitrogen-doped graphene Download PDFInfo
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- CN104229789B CN104229789B CN201410499435.5A CN201410499435A CN104229789B CN 104229789 B CN104229789 B CN 104229789B CN 201410499435 A CN201410499435 A CN 201410499435A CN 104229789 B CN104229789 B CN 104229789B
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Abstract
The present invention relates to the preparation method of a kind of nitrogen-doped graphene, citric acid and two kinds of raw materials of tripolycyanamide are added in methanol, by stirring, ultrasonic, obtain presoma after drying, by presoma point two-section calcining in tube furnace, finally prepare nitrogen-doped graphene.Compared with prior art, raw material sources of the present invention are extensive, and step is simple, low for equipment requirements, and preparation process need not add reducing agent, and environmental pollution is little.The N doped graphene lamella prepared is thin, and specific surface area is big, even structure, favorable reproducibility.
Description
Technical field
The present invention relates to nano-carbon material preparation field, specifically refer to the preparation method of a kind of nitrogen-doped graphene.
Background technology
Graphene be a kind of by carbon atom with sp2What the monoatomic layer that hydridization connects was constituted has monolayer tow-dimensions atom knot
The material with carbon element of structure, because it has physics free from worldly cares and electrochemical properties, such as high-specific surface area, high conductivity, high machine
Tool intensity etc., the most persistently by the extensive concern of scientific circles.Theoretical research shows that N doping can change graphite
The electronic structure of alkene and chemical property, make it have n-type semiconductor character, thus expand its optics, electricity and
The application in the fields such as magnetics.
The most conventional method preparing nitrogen-doped graphene mainly has chemical vapour deposition technique (CVD) and hydro-thermal
Method etc..Wherein CVD needs to use metallic catalyst, its meeting polluted product, is difficult to produce N doping stone in batches
Ink alkene: hydro-thermal method need to use poisonous reducing agent, can produce environment and pollute.In recent years, one used glucose conduct
Carbon source, and with dicyandiamide mixed calcining, the class Graphene carbonitride (g-C that dicyandiamide polycondensation is obtained3N4) conduct
Intermediate templates obtains the method for Graphene and starts to be paid close attention to.Li X H etc. on this basis, prepare
Graphene (Li X H, Antonietti M.Polycondensation of Boron containing the excellent performance of B and N doping
-and Nitrogen-Codoped Holey Graphene Monoliths from Molecules:Carbocatalysts
For Selective Oxidation [J] .Angewandte Chemie International Edition, 2013,52 (17):
4572-4576).The features such as it is simple that the method has synthesis, pollution-free, excellent performance.
Under study for action it was found that citric acid has stronger acidity, salt can be formed with weakly alkaline tripolycyanamide.It is subject to
The inspiration of above-mentioned work, this salt is likely to become the carbon source preparing Graphene.If a small amount of citric acid is added
In tripolycyanamide, salt can be formed and be evenly distributed on formation presoma in excessive tripolycyanamide, calcined
Cheng Zhong, tripolycyanamide polycondensation obtains g-C3N4, and salt decomposes the carbon produced and is evenly distributed on g-C3N4On；Enter one
In step high-temperature burning process, g-C3N4Decompose, but its layer structure can be attached carbon in the above and retain and shape
One-tenth Graphene, and g-C3N4Decompose the nitrogen source left over can adulterate in entrance Graphene, thus be expected to obtain performance
Excellent nitrogen-doped graphene.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide one to have lamella,
Specific surface area is big, the preparation method of the Graphene of even structure, and its preparation process is simple, environmental protection, and low cost can
The preparation method of the nitrogen-doped graphene of large-scale production.
The purpose of the present invention can be achieved through the following technical solutions: the preparation method of a kind of nitrogen-doped graphene,
It is characterized in that, citric acid and two kinds of raw materials of tripolycyanamide are added in methanol, by stirring, ultrasonic, after drying
Obtain presoma, by presoma point two-section calcining in tube furnace, finally prepare nitrogen-doped graphene.
Described presoma prepares in the following manner: by citric acid and tripolycyanamide be in molar ratio
1: 40～1: 20 joins in absolute methanol solution, stirring 10～30min under room temperature, the most ultrasonic 10～20min,
Take out after sample at 60～80 DEG C of heating in water bath and stir to sample without obvious liquid water, being dried in moving into baking oven,
Obtain required precursor samples.
The addition of described absolute methanol is: every gram of citric acid adds 70～150mL absolute methanols.
The instrument of described ultrasonic employing is probe type ultrasonic processor, and frequency is 20kHz, and power is
200～400W.
The speed of described stirring is 600～1000r/mm.
Described dry refer to be dried at a temperature of 60～80 DEG C 24～48h.
A described point two-section calcining refers to be placed on by presoma in ship type crucible with a lid, is placed in tube furnace, lazy
Property atmosphere under be warming up to 500～600 DEG C with 2～6 DEG C/min, be incubated 2～3h；Then with 3～7 DEG C/min
It is warming up to 800～1000 DEG C, insulation 1～2h, natural cooling, obtain final products.
Compared with prior art, citric acid and tripolycyanamide are reacted the salt obtained as carbon source by the present invention first, and
By stirring, effect such as ultrasonic grade makes this salt and tripolycyanamide form uniform presoma so that at high-temperature burning process
The carbon that middle salt is decomposed to form can be evenly distributed to intermediate die plate g-C3N4On, thus g-C in higher temperature3N4
During decomposition, carbon leaves over g-C3N4Class Graphene layer structure form Graphene, and g-C3N4Decompose the nitrogen of residual
Source doping enters in Graphene, thus it is uniform to obtain pattern, the nitrogen-doped graphene of excellent performance.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of nitrogen-doped graphene of the present invention；
Fig. 2 is the XRD figure of nitrogen-doped graphene of the present invention；
Fig. 3 is the Raman spectrogram of nitrogen-doped graphene of the present invention.
Detailed description of the invention
Elaborating embodiments of the invention below, the present embodiment enters under premised on technical solution of the present invention
Row is implemented, and gives detailed embodiment and concrete operating process, but under protection scope of the present invention is not limited to
The embodiment stated.
Embodiment 1
The first step, prepares presoma and specifically comprises the following steps that described presoma prepares in the following manner: take
1.1g citric acid and 28.9g tripolycyanamide (mol ratio is 1: 40), add in 150ml absolute methanol, room temperature
Under stir 10min with the speed of 1000r/min, sample is put in probe type ultrasonic processor, 20kHz, 400
Ultrasonic 10min in ice-water bath under the power of W.Sample after ultrasonic is taken out, at 80 DEG C heating in water bath and with
The speed stirring of 1000r/min without obvious liquid water, moves in blast dry oven to sample, 80 DEG C of dry 24h,
Obtain required presoma.
Second step, presoma calcination process is as follows: the above-mentioned precursor samples that obtains is loaded 100 × 50 × 50cm
Ship type crucible in, close the lid, be placed in tube furnace, under atmosphere of inert gases, with the liter of 6 DEG C/min
Temperature speed, to 600 DEG C of calcining 2h, then calcines 1h with the heating rate of 7 DEG C/min to 1000 DEG C, natural
Cooling.
3rd step, takes out above-mentioned post-calcination sample, obtains nitrogen-doped graphene.
As shown in Figures 1 to 3, by the test analysis such as XRD, SEM, BET, Raman, elementary analysis, system
The standby sample obtained is nitrogen-doped graphene, and hole size is 2.24cm3/ g, specific surface area is 909m2/ g, nitrogenous
Amount is 11.3%.
Embodiment 2
The first step, prepares presoma and specifically comprises the following steps that described presoma prepares in the following manner: take
1.2g citric acid and 23.8g tripolycyanamide (mol ratio is 1: 30), add in 130ml absolute methanol, room temperature
Under stir 20min with the speed of 800r/min, sample is put in probe type ultrasonic processor, 20kHz, 300
Ultrasonic 15min in ice-water bath under the power of W.Sample after ultrasonic is taken out, at 70 DEG C heating in water bath and with
The speed stirring of 800r/min without obvious liquid water, moves in blast dry oven to sample, 70 DEG C of dry 36h,
Obtain required presoma.
Second step, presoma calcination process is as follows: the above-mentioned precursor samples that obtains is loaded 100 × 50 × 50cm
Ship type crucible in, close the lid, be placed in tube furnace, under atmosphere of inert gases, with the liter of 4 DEG C/min
Temperature speed, to 550 DEG C of calcining 2.5h, then calcines 1.5h with the heating rate of 5 DEG C/min to 900 DEG C, from
So cooling.
3rd step, takes out above-mentioned post-calcination sample, obtains nitrogen-doped graphene.
By test analysis such as XRD, SEM, BET, Raman, elementary analysiss, the sample prepared is
Nitrogen-doped graphene, average pore sizes is 1.05cm3/ g, specific surface area is 370m2/ g, nitrogen content is 25.5%.
Embodiment 3
The first step, prepares presoma and specifically comprises the following steps that described presoma prepares in the following manner: take
1.4g citric acid and 18.6g tripolycyanamide (mol ratio is 1: 20), add in 100ml absolute methanol, room temperature
Under stir 30min with the speed of 600r/min, sample is put in probe type ultrasonic processor, 20kHz, 200
Ultrasonic 20min in ice-water bath under the power of W.Sample after ultrasonic is taken out, at 60 DEG C heating in water bath and with
The speed stirring of 600r/min without obvious liquid water, moves in blast dry oven to sample, 60 DEG C of dry 48h,
Obtain required presoma.
Second step, presoma calcination process is as follows: the above-mentioned precursor samples that obtains is loaded 100 × 50 × 50cm
Ship type crucible in, close the lid, be placed in tube furnace, under atmosphere of inert gases, with the liter of 2 DEG C/min
Temperature speed, to 500 DEG C of calcining 3h, then calcines 2h with the heating rate of 3 DEG C/min to 800 DEG C, the coldest
But.
3rd step, takes out above-mentioned post-calcination sample, obtains nitrogen-doped graphene.
By test analysis such as XRD, SEM, BET, Raman, elementary analysiss, the sample prepared is
Nitrogen-doped graphene, average pore sizes is 0.90cm3/ g, specific surface area is 423m2/ g, nitrogen content is 26.3%.
Claims (6)
1. the preparation method of a nitrogen-doped graphene, it is characterised in that citric acid and two kinds of raw materials of tripolycyanamide are added in methanol, by stirring, ultrasonic, obtain presoma after drying, by presoma point two-section calcining in tube furnace, finally prepare nitrogen-doped graphene；
Described presoma prepares in the following manner: join in absolute methanol for 1:40～1:20 in molar ratio by citric acid and tripolycyanamide, 10～30min are stirred under room temperature, the most ultrasonic 10～20min, take out after sample at 60～80 DEG C of heating in water bath and stir to sample without obvious liquid, it is dried in moving into baking oven, obtains required precursor samples.
The preparation method of a kind of nitrogen-doped graphene the most according to claim 1, it is characterised in that the addition of described absolute methanol is: every gram of citric acid adds 70～150mL absolute methanols.
The preparation method of a kind of nitrogen-doped graphene the most according to claim 1, it is characterised in that the instrument of described ultrasonic employing is probe type ultrasonic processor, frequency is 20kHz, and power is 200～400W.
The preparation method of a kind of nitrogen-doped graphene the most according to claim 1, it is characterised in that the speed of described stirring is 600～1000r/min.
The preparation method of a kind of nitrogen-doped graphene the most according to claim 1, it is characterised in that described dry refer to be dried at a temperature of 60～80 DEG C 24～48h.
The preparation method of a kind of nitrogen-doped graphene the most according to claim 1, it is characterized in that, a described point two-section calcining refers to be placed on by presoma in ship type crucible with a lid, is placed in tube furnace, it is warming up to 500～600 DEG C with 2～6 DEG C/min under atmosphere of inert gases, is incubated 2～3h；Then it is warming up to 800～1000 DEG C with 3～7 DEG C/min, insulation 1～2h, natural cooling, obtain final products.
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